JP2006124448A - Crystallization inhibitor of oils and fats, oils and fats and food - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crystallization inhibitor for oils and fats exerting excellent crystallization inhibitory effect against crystal deposition in the oils and fats, the fats and oils and food. <P>SOLUTION: The crystallization inhibitor for oils and fats is a polyglycerol fatty acid ester comprising erucic acid and stearic acid as essential constituent fatty acids. In the constituent fatty acids, the molar ratio of erucic acid to the total of erucic acid and stearic acid is preferably ≥0.50. The crystallization inhibitor for oils and fats is added to the oils and fats. The food is manufactured using the oils and fats. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a crystallization inhibitor for fats and oils that suppresses crystallization of fats and oils, fats and oils, and foods.

  Liquid and solid fats and oils are partly or entirely crystallized due to a decrease in ambient temperature. At this time, there is a problem of deteriorating the appearance, flavor and texture of foods produced using fats and oils. In addition, in oil-in-water emulsified foods produced using fats and oils, when stored at low temperatures or when thawed after freezing, there is a problem that the emulsification of the food breaks and separates into an oil phase and an aqueous phase . This problem of separation into an oil phase and an aqueous phase is caused by the integration of neighboring oils and fats, but the integration of neighboring oils and fats causes crystals to precipitate and grow in the oil and fat dispersed in water by emulsification. However, it is considered that the main factor is that the crystals break through the aqueous phase and come into contact with neighboring fats and oils.

In order to solve the problems caused by crystal precipitation in these fats and oils, it is first necessary to suppress the formation of crystals in the fats and oils, and secondly, the precipitated crystals grow. It is necessary to suppress. For this reason, it has been conventionally practiced to contain polyglycerin fatty acid esters in fats and oils to suppress crystal precipitation and growth. For example, Patent Document 1 discloses a polyglycerol fatty acid ester that suppresses crystal precipitation, and Patent Document 2 discloses a polyglycerol fatty acid ester that suppresses crystal growth.
Japanese Patent Application Laid-Open No. 2002-212587 JP-A-9-124297

  The crystallization inhibitor for fats and oils disclosed in Patent Document 1 is a polyglycerin fatty acid ester. In the constituent fatty acid of this ester, erucic acid is 40% by weight or more, and other constituent fatty acids are carbons other than erucic acid. It is disclosed that the number is 8 to 22 fatty acids.

  On the other hand, in Patent Document 2, a polyglycerin fatty acid ester is used as a crystal growth inhibitor in order to suppress the formation of crystals in the oil of mayonnaise, which is a kind of oil-in-water emulsified food, and the growth and destruction of the emulsion. Is added to fats and oils. And as for the polyglyceryl fatty acid ester added to fats and oils, it is disclosed that an unsaturated fatty acid having 8 to 22 carbon atoms occupies 5 to 50% of the total fatty acid amount and HLB is 3 or less as a fatty acid constituting this ester. ing.

  However, the storage temperature of fats and oils and foods that has been conventionally required was 5 to 15 ° C. assuming cold regions and freezers, but today, when fats and oils are used for frozen foods, −20 to −25. May be stored at a temperature of ℃. When foods manufactured using fats and oils and fats at temperatures of -20 to -25 ° C are stored, crystals will precipitate even in fats and foods to which known polyglycerin fatty acid esters are added. .

  In addition, as the storage temperature of fats and oils and foods decreases, the period of fats and foods decays and deteriorates, so the storage period of fats and oils and the like has become longer. The prolonged storage period is likely to cause a situation where crystals are precipitated in the oil.

  In view of the problem of crystal precipitation in fats and oils, an object of the present invention is to provide a crystallization inhibitor for fats and oils that exhibits an excellent crystallization inhibitory effect on crystal precipitation. Moreover, it is an object of the present invention to provide fats and oils containing this crystallization inhibitor for fats and oils and foods produced using these fats and oils.

  Based on the knowledge that polyglycerin fatty acid ester having fatty acids other than erucic acid and stearic acid has a crystallization inhibitory effect by making erucic acid and stearic acid essential fatty acids. The present invention has been completed.

  That is, the present invention is a crystallization inhibitor for fats and oils comprising a polyglycerin fatty acid ester that suppresses crystallization of fats and oils, and has erucic acid and stearic acid as constituent fatty acids of the polyglycerin fatty acid ester. It is a characteristic crystallization inhibitor for fats and oils.

  In the constituent fatty acid, the molar ratio of erucic acid in the total molar amount of erucic acid and stearic acid is preferably 0.50 or more. The esterification rate of the polyglycerin fatty acid ester is preferably 80% or more. When the esterification rate is 80% or more, the emulsification destruction suppressing effect of the emulsified food is excellent. Here, the esterification rate is the average degree of polymerization of polyglycerol calculated from the hydroxyl value (n), the number of hydroxyl groups of this polyglycerol (n + 2), and the number of moles of branched fatty acids to be added (M). (M / (n + 2)) × 100 = value calculated by esterification rate (%).

  Moreover, this invention is the foodstuff manufactured using the fats and oils which contained the said crystallization inhibitor for fats and oils, and this fats and oils. This food may be a dressing.

  According to the crystallization inhibitor configured as described above, by including a specific combination of erucic acid and stearic acid in the constituent fatty acid of the polyglycerin fatty acid ester, the excellent crystallization inhibitory effect of fats and oils can be obtained. Demonstrate.

  Further, according to the fat and oil configured as described above, since the crystallization of the fat and oil is suppressed by containing a polyglycerin fatty acid ester that exhibits an excellent crystallization inhibitory effect, the appearance, flavor and texture are deteriorated. It becomes a suppressed oil and fat. Moreover, the foodstuff comprised as mentioned above turns into a foodstuff by which the external appearance, the flavor, and the deterioration of the food texture were suppressed.

  Hereinafter, the present invention will be described based on embodiments. The crystallization inhibitor in the present embodiment is a polyglycerol fatty acid ester obtained by esterifying polyglycerol and a fatty acid, and is used as a crystallization inhibitor that suppresses oil and fat crystallization.

The polyglycerin is not particularly limited, but polyglycerin having an average degree of polymerization calculated from the hydroxyl value of 2 to 20 may be used. In this specification, the average degree of polymerization (n) calculated from the hydroxyl value is a value calculated by terminal analysis, and is calculated from the following formulas (formula 1) and (formula 2).
(Formula 1) Molecular weight = 74n + 18
(Formula 2) Hydroxyl value = 56110 (n + 2) / Molecular weight The hydroxyl value is a numerical value that is an index of the number of hydroxyl groups contained in the esterified product, and the free hydroxyl group contained in 1 g of the esterified product is acetylated. This refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid required for the conversion to potassium. The milligrams of potassium hydroxide are compiled by the Japan Oil Chemists 'Society, “Established by the Japan Oil Chemists' Society, Standard Oil Analysis Test. Law (I), 1996 edition ".

  The fatty acid is a constituent fatty acid of the polyglycerol fatty acid ester, and erucic acid and stearic acid are essential fatty acids. Polyglycerin fatty acid ester produced using erucic acid and fatty acids other than stearic acid as essential fatty acids only exhibits the same degree of crystallization inhibition effect as polyglycerin fatty acid ester produced using erucic acid, Polyglycerin fatty acid esters produced using erucic acid and stearic acid as essential fatty acids exhibit a crystallization inhibitory effect superior to polyglycerin fatty acid esters produced simply using erucic acid.

  As long as erucic acid and stearic acid are essential fatty acids, the fatty acid may contain one or more other fatty acids. Although this other fatty acid is not specifically limited, It is good in it being C8-C22 saturated fatty acid and unsaturated fatty acid. Examples of saturated fatty acids having 8 to 22 carbon atoms include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, arachidic acid, and behenic acid. On the other hand, examples of unsaturated fatty acids having 8 to 22 carbon atoms include decenoic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, arachidonic acid, sardine acid, docosapentaenoic acid, and docosahexaenoic acid.

  The erucic acid that is the constituent fatty acid of the ester is not particularly limited in the erucic acid content in the constituent fatty acid, but the molar ratio of erucic acid in the total molar amount of erucic acid and stearic acid that are the constituent fatty acids is It is suitable that it is 0.50 or more. This is because, when the molar ratio of erucic acid is 0.50 or more, the crystallization suppressing effect for suppressing crystal precipitation is remarkably improved. A more preferable molar ratio of erucic acid is 0.55 or more. When the molar ratio is 0.55 or more, not only the crystallization inhibitory effect but also the crystallization inhibitory effect superior to the polyglycerol fatty acid ester produced simply using erucic acid is exhibited, and the oil-in-water emulsion food The effect of suppressing the emulsion breakage is also superior to that of an ester having erucic acid as a constituent fatty acid.

  The esterification rate of the polyglycerol fatty acid ester is preferably 80% or more. The esterification rate is the average degree of polymerization of polyglycerol (n) calculated from the hydroxyl value, the number of hydroxyl groups of this polyglycerol (n + 2), and the number of moles of branched fatty acids to be added (M). / (N + 2)) × 100 = value calculated by esterification rate (%). When the esterification rate is 80% or more, the emulsification destruction suppressing effect is significantly higher than that of the polyglycerin fatty acid ester having an esterification rate of less than 80%. The emulsion breakage inhibiting effect is better as the esterification rate is closer to 100%, more preferably 90% or more, and even more preferably 95% or more.

  The polyglycerol fatty acid ester can be produced, for example, by the following method. A fatty acid is charged into polyglycerin, and an alkali catalyst such as sodium hydroxide is added to the polyglycerin charged with this fatty acid, and then an esterification reaction is carried out under ordinary pressure or reduced pressure. The fatty acid is preferably charged with at least erucic acid and stearic acid. The esterification reaction is performed until almost all of the charged fatty acid is esterified. That is, the reaction is sufficiently performed until almost no free fatty acid is consumed.

  By adding the polyglycerol in this embodiment to fats and oils, the crystal precipitation in fats and oils is suppressed. The fats and oils that can suppress crystallization are not particularly limited, and may be animal fats or animal oils that are animal fats or animal oils, or vegetable fats or oils that are vegetable fats or vegetable oils. Examples of animal fats include milk fat, goat milk fat, beef fat, pork fat, and sheep fat. Examples of animal oils include sardine oil, mackerel oil, and shark liver oil. Examples of vegetable fats include palm oil, palm oil, cacao butter, shea fat, and wood wax palm kernel oil. As the vegetable oil, any of dry oil, semi-dry oil and non-dry oil may be used. Examples of the dry oil include linseed oil, tung oil, safflower oil, and grape seed oil. As the semi-dry oil, Examples include soybean oil, corn oil, sesame oil, rapeseed oil, sunflower oil, and cottonseed oil. Examples of non-drying oil include olive oil, mustard oil, camellia oil, castor oil, peanut oil, macadamian nut oil, and hazelnut oil. Moreover, what separated the component fats and oils contained in fats and oils and hydrogenated fats and oils may be sufficient, and fats and oils may be medium chain triglyceride and diglyceride. Moreover, sterol and sterol ester may be added to the fats and oils.

  The fats and oils in this embodiment can be used for foods as well as the fats and oils conventionally used for foods. Examples of the food include margarine, confectionery, and mayonnaise, and also include an oil-in-water emulsion food that is a food obtained by emulsifying and dispersing oils and fats in water such as dressing.

  EXAMPLES Hereinafter, although this invention is shown concretely based on an Example, this invention is not limited to an Example. The erucic acid used in the examples and comparative examples was erucic acid having a purity of 88% by weight and having a saturated fatty acid of 1% by weight or less and containing substantially no stearic acid. .

Example 1
A polyglycerin fatty acid ester was obtained by mixing 357 g of erucic acid and 150 g of stearic acid with 100 g of polyglycerin having an average degree of polymerization of 10 and reacting at 250 ° C. under an alkaline catalyst and a nitrogen stream.

(Example 2)
A polyglycerin fatty acid ester was obtained in the same manner as in Example 1 except that 357 g of erucic acid, 75 g of stearic acid, and 68 g of palmitic acid were used as fatty acids.

(Comparative Example 1)
A polyglycerol fatty acid ester was obtained in the same manner as in Example 1 except that 357 g of erucic acid and 135 g of palmitic acid were used as the fatty acid.

(Comparative Example 2)
A polyglycerol fatty acid ester was obtained in the same manner as in Example 1 except that 357 g of erucic acid and 120 g of myristic acid were used as fatty acids.

(Comparative Example 3)
A polyglycerol fatty acid ester was obtained in the same manner as in Example 1 except that 541 g of erucic acid was used as the fatty acid.

  The above Examples 1 and 2 and Comparative Examples 1 to 3 were subjected to a confirmation test for the effect of suppressing crystallization of fats and oils based on the following Test Example 1. In addition, the esterification rate of all the polyglycerol fatty acid esters was 90% or more.

(Test Example 1)
Polyglycerin fatty acid ester was added to rapeseed oil in an amount of 0.1% by weight and heated to 80 ° C. to dissolve. Thereafter, the rapeseed oil in which the polyglycerin fatty acid ester was dissolved was left in a constant temperature bath at 0 ° C., and the number of days required for crystals to precipitate in the rapeseed oil was counted. The results are shown in Table 1. In addition, the constituent fatty acid numerical value in Table 1 is the molar ratio of each constituent fatty acid in the total constituent fatty acid of the polyglycerol fatty acid ester, and the impurity in erucic acid is also regarded as erucic acid.

表１において、エルカ酸とステアリン酸を使用して製造された実施例１及び２のポリグリセリン脂肪酸エステルは、単にエルカ酸を使用して製造された比較例３のポリグリセリン脂肪酸エステルよりも結晶析出日数を大きく遅延させている。一方、ステアリン酸以外の脂肪酸とエルカ酸を使用して製造された比較例１および２のポリグリセリン脂肪酸エステルは、比較例３のエステルと差のない結晶析出日数となっている。つまり、エルカ酸とステアリン酸を必須の構成脂肪酸としているポリグリセリン脂肪酸エステルのみが、結晶析出日数が延長されており、油脂の結晶析出抑制効果に優れていることを確認することができる。

In Table 1, the polyglycerin fatty acid esters of Examples 1 and 2 produced using erucic acid and stearic acid were crystallized more than the polyglycerin fatty acid ester of Comparative Example 3 produced simply using erucic acid. The days are greatly delayed. On the other hand, the polyglycerol fatty acid esters of Comparative Examples 1 and 2 produced using fatty acids other than stearic acid and erucic acid have crystal precipitation days that are not different from the esters of Comparative Example 3. That is, it can be confirmed that only the polyglycerin fatty acid ester having erucic acid and stearic acid as essential constituent fatty acids has an extended crystal precipitation day and is excellent in the effect of suppressing oil crystal precipitation.

  Moreover, the ester of the following Examples 3-5 and the ester of the comparative example 4 were prepared.

(Example 3)
Polyglycerin was obtained in the same manner as in Example 1 except that 268 g of erucic acid and 224 g of stearic acid were used as fatty acids.

Example 4
Polyglycerin was obtained in the same manner as in Example 1 except that 322 g of erucic acid and 180 g of stearic acid were used as fatty acids.

(Example 5)
Polyglycerin was obtained in the same manner as in Example 1 except that 428 g of erucic acid and 90 g of stearic acid were used as fatty acids.

(Comparative Example 4)
Polyglycerin was obtained in the same manner as in Example 1 except that 449 g of stearic acid was used as the fatty acid.

  The esterification rates of the polyglycerin fatty acid esters of Examples 3 to 5 and Comparative Example 4 were 90% or more. About the confirmation test of the crystallization inhibitory effect of ester of Examples 3-5 and Comparative Example 4, it carried out like Test Example 1. Moreover, the confirmation test of the emulsion breakage suppression effect of Examples 1 and 3 to 5 and the oil-in-water emulsified foods of Comparative Examples 3 and 4 was performed based on the following Test Example 2.

(Test Example 2)
A dressing that is an oil-in-water emulsified food containing the polyglycerin fatty acid ester of Examples 1 and 3 to 5 and Comparative Examples 3 and 4 was prepared, and the prepared dressing was sealed in a sealed container, and -30 After refrigerated storage at a temperature of ° C., it was thawed at room temperature. And the test of the emulsion breakage inhibitory effect of polyglycerin fatty acid ester was done by measuring the number of days when the emulsion breakage in which the water phase and the oil phase of the thawed dressing were separated. The dressing was prepared by gradually adding the oil phase to the aqueous phase while stirring the aqueous phase. In this case, the aqueous phase was prepared by mixing and dissolving 11.0 g of vinegar, 0.2 g of xanthan gum, 1 g of MSW-7S (trade name of Sakamoto Pharmaceutical Co., Ltd.) and 1.5 g of sodium chloride in 10.5 g of water, The phase was prepared by adding 0.8 g of any of the esters of Examples and Comparative Examples to 75 g of soybean salad oil and dissolving at a temperature of 80 ° C.

  Table 2 shows the test results of the crystallization inhibitory effect according to Test Example 1 together with the results of Example 1 and Comparative Example 3. Table 2 shows the test results of the emulsion breakage inhibiting effect of Test Example 2. Moreover, the result of Table 2 is represented by a line graph in FIG. In Table 2, the molar ratio of erucic acid is the ratio of the molar amount of erucic acid to the total molar amount of erucic acid and stearic acid constituting the polyglycerol fatty acid ester, and is a value considering the purity of erucic acid. That is, the molar amount of erucic acid = the erucic acid used (g) × 0.88 / the molecular weight of erucic acid, and the molar ratio of erucic acid is the molar amount of erucic acid / the molar amount of erucic acid and the molar amount of stearic acid. The total molar amount, with the amount.

表２の結晶析出日数において、実施例の析出日数は、いずれも比較例の析出日数よりも長い日数となっている。つまり、ステアリン酸だけ、又は、単にエルカ酸を使用して製造したポリグリセリン脂肪酸エステルは、油脂の結晶化抑制効果が小さく、エルカ酸とステアリン酸を併用して製造したポリグリセリン脂肪酸エステルは、結晶化抑制効果が向上することを確認することができる。

In the crystal precipitation days of Table 2, the precipitation days of the examples are all longer than the precipitation days of the comparative examples. That is, the polyglycerin fatty acid ester produced by using only stearic acid or simply using erucic acid has a small effect of suppressing crystallization of fats and oils, and the polyglycerin fatty acid ester produced by combining erucic acid and stearic acid is It can be confirmed that the oxidization suppressing effect is improved.

  Moreover, in the phase separation days of Table 2, the results of the esters of Examples 1, 4, and 5 in which the molar ratio of erucic acid exceeds 0.55 are better than the results of Comparative Example 3. That is, an ester having a molar ratio of erucic acid exceeding 0.55 has not only the effect of suppressing crystallization of fats and oils, but also the effect of suppressing the demulsification of dressings that are oil-in-water emulsified foods from the ester produced using erucic acid It can be confirmed that the results are good.

  Next, polyglycerin fatty acid esters of Examples 6 to 11 below were prepared, and an emulsion breakage inhibition test was performed in the same manner as in Test Example 2.

  The esters of Examples 6-11 were prepared as follows. A mixed fatty acid of erucic acid and stearic acid having a molar ratio of erucic acid: stearic acid = 2: 1 is mixed with 100 g of polyglycerin having an average degree of polymerization of 10, and reacted at 250 ° C. under an alkali catalyst and a nitrogen stream. The ester was obtained. At this time, the esterification rate of each ester in the Examples was different from each other.

  Table 3 shows the emulsion breakage inhibition tests of the esters of Examples 6 to 11 together with the esterification rate.

表３において、エステル化率が８０％に満たない実施例６及び７の日数は、０日である。これは、ドレッシングを−３０℃の温度で冷凍した直後に解凍しても乳化が破壊したものである。一方、エステル化率が８０％以上である実施例８〜１１のエステルを使用したドレッシングにおいては、冷凍した直後に解凍しても乳化破壊が生じなかった。つまり、エステル化率が８０％を超える場合には、乳化破壊抑制効果が格段に向上することを確認することができる。

In Table 3, the days of Examples 6 and 7 having an esterification rate of less than 80% are 0 days. This is because the emulsification is broken even if the dressing is thawed immediately after being frozen at a temperature of −30 ° C. On the other hand, in the dressings using the esters of Examples 8 to 11 having an esterification rate of 80% or more, even when thawed immediately after freezing, no emulsion breakage occurred. That is, when the esterification rate exceeds 80%, it can be confirmed that the emulsion breakage suppressing effect is remarkably improved.

3 is a line graph showing the results of Table 2.

Claims (6)

A crystallization inhibitor for fats and oils comprising a polyglycerin fatty acid ester which suppresses crystallization of fats and oils, wherein erucic acid and stearic acid are included in the constituent fatty acids of the polyglycerin fatty acid ester. Inhibitor. 2. The crystallization inhibitor for fats and oils according to claim 1, wherein in the constituent fatty acid, the molar ratio of erucic acid in the total molar amount of erucic acid and stearic acid is 0.50 or more. The crystallization inhibitor for fats and oils according to claim 1 or 2, wherein an esterification rate of the polyglycerin fatty acid ester is 80% or more. Oil containing the crystallization inhibitor for oil according to any one of claims 1 to 3. Food manufactured using the fats and oils of Claim 4. The food according to claim 5, wherein the food is a dressing.

Images